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- ItemEnlightening Materials with Photoswitches(Weinheim : Wiley-VCH, 2020) Goulet-Hanssens, Alexis; Eisenreich, Fabian; Hecht, StefanIncorporating molecular photoswitches into various materials provides unique opportunities for controlling their properties and functions with high spatiotemporal resolution using remote optical stimuli. The great and largely still untapped potential of these photoresponsive systems has not yet been fully exploited due to the fundamental challenges in harnessing geometrical and electronic changes on the molecular level to modulate macroscopic and bulk material properties. Herein, progress made during the past decade in the field of photoswitchable materials is highlighted. After pointing to some general design principles, materials with an increasing order of the integrated photoswitchable units are discussed, spanning the range from amorphous settings over surfaces/interfaces and supramolecular ensembles, to liquid crystalline and crystalline phases. Finally, some potential future directions are pointed out in the conclusion. In view of the exciting recent achievements in the field, the future emergence and further development of light-driven and optically programmable (inter)active materials and systems are eagerly anticipated. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemMechanistic Insights into the Triplet Sensitized Photochromism of Diarylethenes(Weinheim : Wiley-VCH, 2020) Fredrich, Sebastian; Morack, Tobias; Sliwa, Michel; Hecht, StefanOperating photoswitchable molecules repetitively and reliably is crucial for most of their applications, in particular in (opto)electronic devices, and related to reversibility and fatigue resistance, which both critically depend on the photoisomerization mechanism defined by the substitution pattern. Two diarylethene photoswitches bearing biacetyl triplet sensitizers either at the periphery or at the core were investigated using both stationary as well as transient UV/Vis absorption spectroscopy ranging from the femtosecond to the microsecond time scale. The diarylethene with two biacetyl moieties at the periphery is switching predominantly from the triplet excited state, giving rise to an enhanced fatigue resistance. In contrast, the diarylethene bearing one diketone at the photoreactive inner carbon atom cyclizes from the singlet excited state and shows significantly higher quantum yields for both cyclization and cycloreversion. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemUsing Active Surface Plasmons in a Multibit Optical Storage Device to Emulate Long-Term Synaptic Plasticity(Weinheim : Wiley-VCH, 2020) Rhim, Seon-Young; Ligorio, Giovanni; Hermerschmidt, Felix; Hildebrandt, Jana; Pätzel, Michael; Hecht, Stefan; List-Kratochvil, Emil J.W.Artificial intelligence takes inspiration from the functionalities and structure of the brain to solve complex tasks and allow learning. Yet, hardware realization that simulates the synaptic activities realized with electrical devices still lags behind computer software implementation, which has improved significantly during the past decade. Herein, the capability to emulate synaptic functionalities by exploiting surface plasmon polaritons (SPPs) is shown. By depositing photochromic switching molecules (diarylethene) on a thin film of gold, it is possible to reliably control the electronic configuration of the molecules upon illumination cycles with UV and visible light. These reversible changes modulate the dielectric function of the photochromic film and thus enable the effective control of the SPP dispersion relation at the molecule/gold interface. The plasmonic device displays fundamental functions of a synapse such as potentiation, depression, and long-term plasticity. The integration of such plasmonic devices in an artificial neural network is deployed in plasmonic neuroinspired circuits for optical computing and data transmission. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemProton-Gated Ring-Closure of a Negative Photochromic Azulene- Based Diarylethene(Weinheim : Wiley-VCH, 2020) Hou, Ian Cheng-Yi; Berger, Fabian; Narita, Akimitsu; Müllen, Klaus; Hecht, StefanProton-responsive photochromic molecules are attractive for their ability to react on non-invasive rapid optical stimuli and the importance of protonation/deprotonation processes in various fields. Conventionally, their acidic/basic sites are on hetero-atoms, which are orthogonal to the photo-active π-center. Here, we incorporate azulene, an acid-sensitive pure hydrocarbon, into the skeleton of a diarylethene-type photoswitch. The latter exhibits a novel proton-gated negative photochromic ring-closure and its optical response upon protonation in both open and closed forms is much more pronounced than those of diarylethene photoswitches with hetero-atom based acidic/basic moieties. The unique behavior of the new photoswitch can be attributed to direct protonation on its π-system, supported by 1H NMR and theoretical calculations. Our results demonstrate the great potential of integrating non-alternant hydrocarbons into photochromic systems for the development of multi-responsive molecular switches. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemHighly Cooperative Photoswitching in Dihydropyrene Dimers(Weinheim : Wiley-VCH, 2020) Liesfeld, Pauline; Garmshausen, Yves; Budzak, Simon; Becker, Jonas; Dallmann, Andre; Jacquemin, Denis; Hecht, StefanWe present a strategy to achieve highly cooperative photoswitching, where the initial switching event greatly facilitates subsequent switching of the neighboring unit. By linking donor/acceptor substituted dihydropyrenes via suitable π-conjugated bridges, the quantum yield of the second photochemical ring-opening process could be enhanced by more than two orders of magnitude as compared to the first ring-opening. As a result, the intermediate mixed switching state is not detected during photoisomerization although it is formed during the thermal back reaction. Comparing the switching behavior of various dimers, both experimentally and computationally, helped to unravel the crucial role of the bridging moiety connecting both photochromic units. The presented dihydropyrene dimer serves as model system for longer cooperative switching chains, which, in principle, should enable efficient and directional transfer of information along a molecularly defined path. Moreover, our concept allows to enhance the photosensitivity in oligomeric and polymeric systems and materials thereof. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemOligothiophene-Based Phosphonates for Surface Modification of Ultraflat Transparent Conductive Oxides(Weinheim : Wiley-VCH, 2020) Timpel, Melanie; Nardi, Marco V.; Wegner, Berthold; Ligorio, Giovanni; Pasquali, Luca; Hildebrandt, Jana; Pätzel, Michael; Hecht, Stefan; Ohta, Hiromichi; Koch, NorbertThe self-assembly of electroactive organic molecules on transparent conductive oxides is a versatile strategy to engineer the interfacial energy-level alignment and to enhance charge carrier injection in optoelectronic devices. Via chemical grafting of an aromatic oligothiophene molecule by changing the position of the phosphonic acid anchoring group with respect to the organic moiety (terminal and internal), the direction of the main molecular dipole is changed, i.e., from parallel to perpendicular to the substrate, to study the molecular arrangement and electronic properties at the organic–inorganic interface. It is found that the observed work function increase cannot solely be predicted based on the calculated molecular dipole moment of the oligothiophene-based phosphonates. In addition, charge transfer from the substrate to the molecule has to be taken into account. Molecular assembly and induced electronic changes are analogous for both indium-tin oxide (ITO) and zinc oxide (ZnO), demonstrating the generality of the approach and highlighting the direct correlation between molecular coverage and electronic effects. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemAvoiding the Center-Symmetry Trap: Programmed Assembly of Dipolar Precursors into Porous, Crystalline Molecular Thin Films(Weinheim : Wiley-VCH, 2021) Nefedov, Alexei; Haldar, Ritesh; Xu, Zhiyun; Kühner, Hannes; Hofmann, Dennis; Goll, David; Sapotta, Benedikt; Hecht, Stefan; Krstić, Marjan; Rockstuhl, Carsten; Wenzel, Wolfgang; Bräse, Stefan; Tegeder, Petra; Zojer, Egbert; Wöll, ChristofLiquid-phase, quasi-epitaxial growth is used to stack asymmetric, dipolar organic compounds on inorganic substrates, permitting porous, crystalline molecular materials that lack inversion symmetry. This allows material fabrication with built-in electric fields. A new programmed assembly strategy based on metal-organic frameworks (MOFs) is described that facilitates crystalline, noncentrosymmetric space groups for achiral compounds. Electric fields are integrated into crystalline, porous thin films with an orientation normal to the substrate. Changes in electrostatic potential are detected via core-level shifts of marker atoms on the MOF thin films and agree with theoretical results. The integration of built-in electric fields into organic, crystalline, and porous materials creates possibilities for band structure engineering to control the alignment of electronic levels in organic molecules. Built-in electric fields may also be used to tune the transfer of charges from donors loaded via programmed assembly into MOF pores. Applications include organic electronics, photonics, and nonlinear optics, since the absence of inversion symmetry results in a clear second-harmonic generation signal.
- ItemSimultaneous Effect of Ultraviolet Radiation and Surface Modification on the Work Function and Hole Injection Properties of ZnO Thin Films(Weinheim : Wiley-VCH, 2020) Raoufi, Meysam; Hörmann, Ulrich; Ligorio, Giovanni; Hildebrandt, Jana; Pätzel, Michael; Schultz, Thorsten; Perdigon, Lorena; Koch, Norbert; List-Kratochvil, Emil; Hecht, Stefan; Neher, DieterThe combined effect of ultraviolet (UV) light soaking and self-assembled monolayer deposition on the work function (WF) of thin ZnO layers and on the efficiency of hole injection into the prototypical conjugated polymer poly(3-hexylthiophen-2,5-diyl) (P3HT) is systematically investigated. It is shown that the WF and injection efficiency depend strongly on the history of UV light exposure. Proper treatment of the ZnO layer enables ohmic hole injection into P3HT, demonstrating ZnO as a potential anode material for organic optoelectronic devices. The results also suggest that valid conclusions on the energy-level alignment at the ZnO/organic interfaces may only be drawn if the illumination history is precisely known and controlled. This is inherently problematic when comparing electronic data from ultraviolet photoelectron spectroscopy (UPS) measurements carried out under different or ill-defined illumination conditions. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim